Novel pesticidal 1-(alkyl-phenoxy-aryl)-3-benzoyl ureas and process for preparation

ABSTRACT

Novel 1-(alkylphenoxyphenyl)-3-benzoyl ureas and a process for their preparation are provided. The novel ureas are useful as the active toxicant in pesticidal composition.

This is a continuation of co-pending application Ser. No. 495,331, filedon May 20, 1983, now abandoned, which is a continuation-in-part of U.S.patent application Ser. No. 393,553 filed June 30, 1982.

FIELD OF INVENTION

This invention relates in general to novel1-(alkyl-phenoxyaryl)-3-benzoyl ureas and to a process for theirpreparation. In one aspect, this invention relates to benzoyl ureaswhich are useful as pesticides.

BACKGROUND OF THE INVENTION

Prior to the present invention a few benzoyl ureas had been reported inthe patent literature as having pesticidal activity. For example, U.S.Pat. No. 3,992,553 which issued on Nov. 16, 1976, and U.S. Pat. No.4,041,177 which issued on Aug. 9, 1977, both disclosed certainbenzoylureido-diphenyl ethers which were indicated to possessinsecticidal properties. Similarly, U.S. Pat. Nos. 3,748,356 and3,933,908 also disclosed certain substituted benzoyl ureas and statedthat the compositions had strong insecticidal activity. U.S. Pat. No.4,148,902 which issued Apr. 10, 1979 discloses substituted((phenylamino)carbonyl) pyridine carboxamides and claims a method ofcontrolling insects in addition to the compositions themselves.Additional disclosures of benzoyl ureas in the patent literature arefound in U.S. Pat. Nos. 4,166,124; 4,083,977; 4,160,834; 4,264,605;4,064,267; and 4,005,223; 4,123,449; 4,068,002; 4,194,005; 4,275,077;4,173,639; 3,989,842; Ger. Offen. 2,901,334 (EP 013-414); and DE3,104,407 (EP 57-888).

Accordingly, one or more of the following objects can be achieved by thepractice of this invention. It is an object of this invention to providenovel 1-(alkylphenoxyaryl)-3-benzoyl ureas. Another object of thisinvention is to provide certain 1-(alkylphenoxyphenyl)-3-benzoyl ureaswhich exhibit excellent insecticidal activity. A still further object ofthis invention is to provide novel benzoyl ureas, such as,1-[2,4-dimethylphenoxy-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,1-[4-(2,5-dimethyl-4-chlorophenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,etc. Another object is to provide processes for the preparation of thenovel benzoyl ureas. A further object is to provide novel pesticidalcompositions containing the novel benzoyl ureas as the active toxicant.Another object of the invention is to provide a method for controllingpests by the application of the novel pesticidal compositions. These andother objects will readily become apparent to those skilled in the artin the light of the teachings herein set forth.

SUMMARY OF THE INVENTION

In its broad aspect the invention relates to novel1-(alkylphenoxyaryl)-3-benzoyl ureas, pesticidal compositions containingthe same, and processes for their preparation and use. The benzoyl ureasof this invention can be represented by the following formula: ##STR1##Wherein X, X' are independently hydrogen, halogen, C₁ -C₄ alkyl,haloalkyl, polyhaloalkyl, alkoxy, polyhaloalkoxy

Y represents oxygen or sulfur;

m, n are 0-4;

R₁ represents halogen, C₁ -C₄ alkyl, haloalkyl, polyhaloalkyl, alkoxy,

R₂ represents halogen, C₁ -C₄ alkyl, polyhaloalkyl, polyhaloalkoxy, C₁-C₈ alkylsulfonyl, C₁ -C₈ alkoxy, C₁ -C₈ alkylthio, C₁ -C₈ dialkylamino,CN, NO₂, CO₂ R₄, CONHR₄ wherein R₄ represents C₁ -C₈ alkyl; and

represents C₁ -C₁₂ alkyl, with the proviso that m may not be 0 or 1 whenn is less than 2.

DETAILED DESCRIPTION OF THE INVENTION

As indicated above, the invention relates to novel1-(alkyl-phenoxyaryl)-3-benzoyl ureas, pesticidal compositionscontaining the same, and processes for their preparation and use.

Preferred benzoyl urea compounds within the broad generic formula 1 arethose having the formulas: ##STR2## wherein X, X¹, Y, R₁, R₂, R₃, n andm are as indicated above.

Particularly preferred benzoyl ureas are those of the formulas: ##STR3##Wherein X, X', Y, R1, R2 and R3 are as indicated above.

The following benzoyl urea compounds are illustrative of thoseencompassed by the above formulas and which can be prepared by thepractice of this invention:

1-[4-(2-methyl-3,4-dichlorophenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-methyl-3,4-dichlorophenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-chlorobenzoyl)urea,

1-[4-(2-methylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-methylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-dichlorobenzoyl)urea,

1-[4-(2-methylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-chlorobenzoyl)urea

1-[4-(2-methylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-chlorobenzoyl)thiourea,

1-[4-(2-methylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-methylbenzoyl)thiourea,

1-[4-(2-methylphenoxy)-2,3,5,6-tetramethylphenyl]-3-(2,6-dimethylbenzoyl)urea,

1-[4-(2-methylphenoxy)-2,3,5,6-tetramethylphenyl]-3-(2,6-methylbenzoyl)thiourea,

1-[4-(2-methylphenoxy)-2,3,5,6-tetramethylphenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-methylphenoxy)-2,3,5,6-tetramethylphenyl]-3-(2,6-dichlorobenzoyl)urea,

1-[4-(2-methylphenoxy)-2,3,5-trimethylphenyl]-3-(2,6-dichlorobenzoyl)urea,

1-[4-(2-methylphenoxy)-3,5-dichlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-methyl-4-bromophenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-methyl-4-bromophenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-chlorobenzoyl)urea,

1-[4-(2-methyl-4-bromophenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-chlorobenzoyl)thiourea,

1-[4-(2-methyl-4-bromophenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-methylbenzoyl)thiourea,

1-[4-(2-methyl-4-bromophenoxy)-2,3,5,6-tetramethylphenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-methyl-4-bromophenoxy)-2,3,5-tetramethylphenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-methyl-4-bromophenoxy)-3,5-dimethylphenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-methyl-4-bromophenoxy)-3,5-dichlorophenyl]-3-(2-chlorobenzoyl)urea,

1-[4-(2-bromo-4-methylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-bromo-4-methylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-chlorobenzoyl)urea,

1-[4-(2-bromo-4-methylphenoxy)-2,3,5,6-tetramethylphenyl]-3-(2-chlorobenzoyl)urea,

1-[4-(2-bromo-4-methylphenoxy)-3,5-dichlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-bromo-4-methylphenoxy)-3,5-dimethylphenyl]-3-(2-methylbenzoyl)thiourea,

1-[4-(2-methyl-4-t-butylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-methyl-4-t-butylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-chlorobenzoyl)urea,

1-[4-(2-methyl-4-t-butylphenoxy)-2,3,5,6-tetramethylphenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-methyl-4-t-butylphenoxy)-3,5-dichlorophenyl]-3-(2-methylbenzoyl)thiourea,

1-[4-(2-methyl-4-chlorophenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-methyl-4-chlorophenoxy)-3,5-dichlorophenyl]-3-(2-methylbenzoyl)thiourea,

1-[4-(2-methyl-4-chlorophenoxy)-2,3,5,6-tetramethylphenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-methyl-4-chlorophenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-dimethoxybenzoyl)urea,

1-[4-(4-nonylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(4-nonylphenoxy)-2,3,5,6-tetramethylphenyl]-3-(2-chlorobenzoyl)thiourea,

1-[4-(4-nonylphenoxy)-3,5-dichlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(4-nonylphenoxy)-3,5-dimethylphenyl]-3-(2-methylbenzoyl)urea,

1-[4-(2-chloro-4-methylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-chloro-4-methylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-chlorobenzoyl)thiourea,

1-[4-(2-chloro-4-methylphenoxy)-3,5-dichlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-chloro-4-methylphenoxy)-2,3,5,6-tetramethylphenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(3,4,5-trimethylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(3,4,5-trimethylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-chlorobenzoyl)thiourea,

1-[4-(3,4,5-trimethylphenoxy)-2,3,5,6-tetramethylphenyl]-3-(2-methylbenzoyl)thiourea,

1-[4-(3,4,5-trimethylphenoxy)-3,5-dichlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2,3,5-trimethylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-dimethoxybenzoyl)urea,

1-[4-(2,3,5-trimethylphenoxy)-2,3,5,6-tetramethylphenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2,3,5-trimethylphenoxy)-3-i-propylphenyl-3-(2-methylbenzoyl)thiourea,

1-[4-(2,3,5-trimethylphenoxy)-3-trifluoromethylphenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-methyl-4-trifluoromethylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-methyl-4-trifluoromethylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-chlorobenzoyl)thiourea,

1-[4-(2-methyl-4-trifluoromethylphenoxy)-3,5-dichlorophenyl]-3-(2,6-dimethoxybenzoyl)urea,

1-[4-(2-methyl-4-trifluoromethylphenoxy)-2,3,5-trimethylphenyl]-3-(2-methylbenzoyl)thiourea,

1-[4-(2,4-dimethylphenoxy)-2,3,6-trimethylphenyl]-3-(2-chlorobenzoyl)urea,

1-[4-(3,5-dimethylphenoxy)-2,6-dimethylphenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-methyl-4-methoxyphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-methyl-4-dimethylaminophenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-methyl-4-methylthiophenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-methyl-4-methylsulfonylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-methyl-4-dimethylaminophenoxy)-3,5-dimethylphenyl]-3-(2-methylbenzoyl)urea,

1-[4-(2-methyl-4-methoxyphenoxy)-3-chloro-6-methylphenyl]-3-(2-methylbenzoyl)urea,

1-[4-(2-methyl-4-methoxyphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(3,4-dichlorobenzoyl)urea,

1-[4-(2,3-dimethyl-4-bromophenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-chlorobenzoyl)urea,

1-[4-(2,5-dimethyl-4-chlorophenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2,5-dimethylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2,5-dimethylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-chlorobenzoyl)urea,

1-[4-(2,5-dimethyl-4-ethoxycarbonylphenoxy)-3-6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2,5-dimethyl-4-ethoxycarbonylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-chlorobenzoyl)urea,

1-[4-(2-methyl-4-trifluoromethylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-chlorobenzoyl)urea,

1-[4-(2,5-dimethyl-4-trifluoromethylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2,5-dimethyl-4-trifluoromethylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-chlorobenzoyl)urea,

1-[4-(2,5-dimethyl-4-trifluoromethoxyphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2,5-dimethyl-4-trifluoromethylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-chlorobenzoyl)urea,

1-[4-(2,5-dimethyl-4-methoxyphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2,5-dimethyl-4-methoxyphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-chlorobenzoyl)urea,

1-[4-(3,5-dimethyl-4-chlorophenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2,4,5-trimethylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2,4,5-trimethylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-chlorobenzoyl)urea,

1-[4-(2,5-dimethyl-4-bromophenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2,5-dimethyl-4-cyanophenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2,5-dimethyl-4-cyanophenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-chlorobenzoyl)urea,

1-[4-(2-methyl-4-cyanophenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-methyl-4-cyanophenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-chlorobenzoyl)urea,

1-[4-(2,4-dimethylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2,4-dimethylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-chlorobenzoyl)urea,

1-[4-(2,5-dichloro-4-methylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2,5-dichloro-4-methylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-chlorobenzoyl)urea,

1-[4-(2-methyl-4,5-dichlorophenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea,

1-[4-(2-methyl-4,5-dichlorophenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-chlorobenzoyl)urea,

1-[4-(2,5-dimethyl-4-chlorophenoxy)-3-methylphenyl]-3-(2,6-difluorobenzoyl)ureaand the like.

The novel benzoyl ureas of this invention can be conveniently preparedby one or more methods. For example, the compounds of this invention maybe prepared by reacting a alkylphenoxyaniline (9) with a benzoylisocyanate or benzoyl isothiocyanate (10) according to Scheme I.##STR4## Wherein: X, X', Y, R₁, R₂, R₃, m, and n have the meaning givento Formula (1).

Alternatively, the novel compounds may be prepared by the reaction of analkylphenoxyphenylisocyanate (12) with a benzamide (11) according toScheme II. ##STR5## Wherein: X, X', Y, R₁, R₂, R₃, m, and n have themeaning given to Formula (1).

In general, the reactions illustrated in Schemes I and II can be carriedout in organic solvents such as aromatic hydrocarbons halogenatedhydrocarbons and the like. Solvents like toluene and 1,2-dichloroethaneare preferred. These reactions proceed at temperatures ranging from roomtemperature to 150° C.

The intermediates shown in Schemes I and II can be prepared according togenerally accepted procedures. Thus, the substituted benzoyl isocyanate(10) can be prepared from the corresponding benzamide following thegeneral procedure of Speziale et. al., J. Org. Chem. 27, 3742 (1962).##STR6##

The substituted benzoyl isothiocyanate (10) can be prepared from thecorresponding acid chloride with potassium thiocyanate. This procedurein general is similar to that employed by Ambelang, et. al J. Amer.Chem. Soc., 61, 632 (1937).

The aniline (9) can be prepared according to Scheme III shown below.##STR7## Wherein R₁, R₂, R₃, m and n have the meaning given to Formula1.

The reaction of substituted chloronitrobenzene (13) with substitutedphenol (14) proceeds in the presence of base at elevated temperature togive the substituted nitroether (15). The reduction of nitroether (15)to aniline (9) can be achieved under hydrogen atmosphere using aheterogeneous hydrogenation catalyst. Suitable catalyst includesplatinum or palladium on carbon or Raney nickel. The pressure rangingfrom 20˜100 PSI at ambient temperature can be applied. Suitable solventsinclude aromatic hydrocarbon or alcohol. The reduction of nitroether(15) to aniline (9) can also be achieved by chemical method using theprocedure of E. Enders, et. al., British patent 1,456,964.

The intermediates such as substituted chloronitrobenzene and substitutedphenol are available commercially or may be prepared by well knownmethod from chemical literature.

One particular chloronitrobenzene (16) was prepared by the routeoutlined in Scheme IV. ##STR8##

The aniline (9) can be converted to the isocyanate or isothiocyanate(12) by the reaction with phosgene or thiophosgene as shown below:##STR9## Wherein: Y, R₁, R₂,R₃, m, and n have the meaning given toFormula 1.

The compounds contemplated in this invention may be employed asinsecticides according to methods known to those skilled in the art.Pesticidal compositions containing the compounds as the active toxicantwill usually comprise a carrier and/or diluent, either liquid or solid.

Suitable liquid diluents or carriers include water, pertroleumdistillates, or other liquid carriers with or without surface activeagents. Liquid concentrates may be prepared by dissolving one of thesecompounds with a nonphytotoxic solvent such as acetone, xylene,nitrobenzene, cyclohexanone or dimethyl formamide and dispersing thetoxicants in water with the aid of suitable surface active emulsifyingand dispersing agents.

The choice of dispersing and emulsifying agents and the amount employedis dictated by the nature of the composition and the ability of theagent to facilitate the dispersion of the toxicant. Generally, it isdesirable to use as little of the agent as is possible, consistent withthe desired dispersion of the toxicant in the spray so that rain does nore-emulsify the toxicant after it is applied to the plant and wash itoff the plant. Nonionic, anionic, or cationic dispersing and emulsifyingagents may be employed, for example, the condensation products ofalkylene oxides with phenol and organic acids, alkyl aryl sulfonates,complex ether alcohols, quaternary ammonium compounds, and the like.

In the preparation of wettable powder or dust or granulatedcompositions, the active ingredient is dispersed in and on anappropriately divided solid carrier such as clay, talc, bentonite,diatomaceous earth, fuller's earth, and the like. In the formulation ofthe wettable powders the aforementioned dispersing agents as well aslignosulfonates can be included.

The required amount of the toxicants comtemplated herein may be appliedper acre treated in from 1to 200 gallons or more of liquid carrierand/or diluent or in from about 5 to 500 pounds of inert solid carrierand/or diluent. The concentration in the liquid concentrate will usuallyvary from about 10 to 95 percent by weight and in the solid formulationsfrom about 0.5 to about 90 percent by weight. Satisfactory sprays,dusts, or granules for general use contain from about 1/4 to 15 poundsof active toxicant per acre.

The pesticides contemplated herein prevent attack by insects upon plantsor other material to which the pesticides are applied, and they haverelatively high residual toxicity. With respect to plants, they have ahigh margin of safety in that when used in sufficient amount to kill orrepel the insects, they do not burn or injure the plant, and they resistweathering which includes wash-off cause by rain, decomposition byultraviolet light, oxidation, or hydrolysis in the presence of moistureor, at least, such decomposition, oxidation, and hydrolysis as wouldmaterially decrease the desirable pesticidal characteristic of thetoxicants or impart undesirable characteristics, for instance,phytotoxicity, to the toxicants. The toxicants are so chemically inertthat they are now compatible with substantially any other constituentsof the spray schedule, and they may be used in the soil, upon the seeds,or the roots of plants without injuring either the seeds or roots ofplants. Mixtures of the active compounds may be employed if desired aswell as combinations of the active compounds of this invention withother biologically active compounds or ingredients.

The following examples illustrate the best mode presently comtemplatedfor the practice of the invention:

EXAMPLE 1 Preparation of4-(2,4-dimethylphenoxy)-3,6-dimethyl-5-chloronitrobenzene

To a flask equipped with condenser, stirrer, under nitrogen, was added3,6-dimethyl-4,5-dichloronitrobenzene (50 g, 0.23 mol),2,4-dimethylphenol (38.5 g, 0.32 mol), potassium carbonate (50 g, 0.36mol), and dimethylformamide (125 ml). The resulting mixture was heatedat 90°˜100° for 72 hours. It was then cooled, filtered, and concentratedto give dark oil. It was partitioned between toluene (300 ml) and 4%sodium hydroxide (250 ml) and then separated. The organic layer waswashed with water and brine, dried (Na₂ SO₄) and concentrated to givedark oil. Solid was formed after the oil was trituated with hexane. Thesolid was washed with cold hexane and vacuum dried to give a tan powder(47.8 g, 0.16 mol); mp 78°˜80°.

Anal: C₁₆ H₁₆ ClNO₃ : Calcd: C, 62.85; H, 5.27; N, 4.58. Found: C,63.47: H, 5.35; N, 4.49.

EXAMPLE 2 A. Preparation of4-(2,4-dimethylphenoxy)-3,6-dimethyl-5-chloroaniline

To a solution of4-(2,4-dimethylphenoxy)-3,6-dimethyl-5-chloronitrobenzene (25 g, 81.8mmol) in toluene (250 ml) was added 5% platinum on carbon (1.0 g). Theresulting mixture was subjected to hydrogenation at 20 psi. After 4.5hours, the reaction mixture was filtered through celite and concentratedto given an oil (24.5 g). It turned to a pinkish solid after high vacuumdrying; mp 86°˜88° C.

Anal: C₁₆ H₁₈ ClNO: Calcd: C, 69.69; H, 6.53; N, 5.08. Found: C, 70.02;H₃ 6.60; N, 5.68.

B. Preparation of4-(3-methyl-4-methylthiophenoxy)-3,6-dimethyl-5-chloroaniline

To a solution of 4-(3-methyl-4-methylthiophenoxy)-3,6-dimethyl-5-chloronitrobenzene (5.0 g, 14.8 mmol) in 7.5 ml of p-dioxanewas added SnCl₂.2H₂ O (10.0 g, 44.4 mmol) and concentrated HCl (10.5ml). The resulting mixture was heated up to reflux for 65 min., cooled,and poured into a mixture of NaOH (20 g), H₂ O (50 ml), and ice (50 g).The mixture was extracted twice with toluene. The combined organicextracts were washed with 4% NaOH, H₂ O, and brine. It was then dried(Na₂ SO₄) and concentrated to yield a yellow oil. Solid formed after theoils was chilled and trituated with cold hexane and a trace of ethylacetate. The solid was filtered and washed with hexane to give a beigepowder (3.06 g, 9.9 mmol); mp 80°-86° C. (decomp.).

Anal: C₁₆ H₁₈ ClNOS: Calcd: C, 62.34; H, 5.89; N, 4.55. Found: C, 62.38;H, 5.89; N, 4.25.

EXAMPLE 3 Preparation of1-(2-Chlorobenzoyl)-3-[4-(2,4-dimethylphenoxy)-3,6-dimethyl-5-chlrophenyl]urea

To a warm solution of 4.94 g (17.9 mmol) of4-(2,4-dimethylphenoxy)-3,6-dimethyl-5-chloroaniline in 12.5 ml oftoluene was added 4.21 g of 2-chlorobenzoyl isocyanate in 1.5 ml oftoluene. The resulting solution was heated at 90° for 0.5 hour. It wasthen cooled and diluted with 5 ml of hexane. The mixture was filteredand the solid was washed with 50% hexane in toluene. A white solid (6.32g, 13.8 mmol) was obtained after vacuum dried at 80° overnight; mp163°-165° C.

Anal: C₂₄ H₂₂ Cl₂ N₂ O₃ : Calcd: C, 63.03; H, 4.85; N, 6.12. Found: C,63.33; H, 4.94; N, 6.09.

EXAMPLES 4-216

In a manner similar to that employed in the preceding examples, andusing of the synthesis schemes previously disclosed, other ureacompounds were prepared. The identity of the substituents on the genericformula and the analytical data are set forth in table I below:

    TABLE I      1-(Alkylphenoxyaryl)-3-Benzoyl Ureas      ##STR10##       Calculated Found Example Molecular Formula XX' Y R.sub.1 R.sub.2     R.sub.3 C H N C H N       1 C.sub.22 H.sub.16 Cl.sub.2 F.sub.2 N.sub.2 O.sub.3 2,6-F.sub.2 O     3,5-Cl 2-CH.sub.3 4-CH.sub.3 56.79 3.47 6.02 56.61 3.35 6.08 2 C.sub.22     H.sub.17 Cl.sub.3 N.sub.2 O.sub.3 2-Cl O 3,5-Cl 2-CH.sub.3 4-CH.sub.3     56.97 3.70 6.04 56.84 3.61 6.02 3 C.sub.22 H.sub.16 Cl.sub.4 N.sub.2     O.sub.3 2,6-Cl.sub.2 O 3,5-Cl 2-CH.sub.3 4-CH.sub.3 53.03 3.24 5.62     52.38 3.15 5.72 4 C.sub.24 H.sub.22 F.sub.2 N.sub.2 O.sub.3 2,6-F.sub.2     O 3,5-(CH.sub.3).sub.2 2-CH.sub.3 4-CH.sub.3 67.91 5.23 6.60 67.23 5.10     6.62 5 C.sub.24 H.sub.22 ClFN.sub.2      O.sub.3 2,6-ClF O 3,5(CH.sub.3).sub.2 2-CH.sub.3 4-CH.sub.3 65.35 5.03     6.35 65.22 5.03 6.29 6 C.sub.24 H.sub.23 ClN.sub.2 O.sub.3 2-Cl O     3,5(CH.sub.3).sub.2 2-CH.sub.3 4-CH.sub.3 68.16 5.47 6.63 68.12 5.58     6.48 7 C.sub.24 H.sub.22 Cl.sub.2 N.sub.2 O.sub.3 2,6-Cl.sub.2 O     3,5(CH.sub.3).sub.2 2-CH.sub.3 4-CH.sub.3 63.02 4.85 6.13 58.72 4.16     6.33 8 C.sub.24 H.sub.22 Cl.sub.2 N.sub.2 O.sub.3 2-Cl O 3,5,6-CH.sub.3     ClCH.sub.3 2-Ch.sub.3 4-CH.sub.3 63.03 4.85 6.12 63.33 4.94 6.09 9     C.sub.24 H.sub.21 Cl.sub.3 N.sub.2 O.sub.3 2,6-Cl.sub.2 O 3,5,6-CH.sub.3     ClCH.sub.3 2-CH.sub.3 4-CH.sub.3 58.61 4.30 5.70 58.28 4.21 5.64 10     C.sub.24 H.sub.21 Cl.sub.2 FN.sub.2 O.sub.3 2,6-ClF O 3,5,6-CH.sub.3     ClCH.sub.3 2-CH.sub.3 4-CH.sub.3 60.64 4.45 5.89 60.79 4.42 5.82 11     C.sub.24 H.sub.21 ClF.sub. 2 N.sub.2      O.sub.3 2,6-F.sub.2 O 3,5,6-CH.sub.3 ClCH.sub.3 2-CH.sub.3 4-CH.sub.3     62.82 4.61 6.10 62.94 4.88 6.03 12 C.sub.22 H.sub.15 Cl.sub.5 N.sub.2     O.sub.3 2-Cl O 3,5-Cl.sub.2 2,3,4-CH.sub.3 ClCl 5-CH.sub.3 49.61 2.84     5.26 49.99 2.90 5.21 13 C.sub.22 H.sub.14 Cl.sub.6 N.sub.2 O.sub.3     2,6-Cl.sub.2 O 3,5-Cl.sub.2 2,3,4-CH.sub.3 ClCl 5-CH.sub.3 46.60 2.49     4.94 46.74 2.53 4.94 14 C.sub.22 H.sub.14 Cl.sub.5 FN.sub.2 O.sub.3     2,6-ClF O 3,5-Cl.sub.2 2,3,4-CH.sub.3 ClCl 5-CH.sub.3 47.99 2.56 5.09     47.21 2.80 5.01 15 C.sub.22 H.sub.14 Cl.sub.4 F.sub.2 N.sub.2 O.sub.3     2,6-F.sub.2 O 3,5-Cl.sub.2 2,3,4-CH ClCl 5-CH.sub.3 49.47 2.64 5.24     49.44 2.74 5.17 16 C.sub.24 H.sub.22 Cl.sub.2 N.sub.2 O.sub.2 S 2-Cl S     3,5,6-CH.sub.3 ClCH.sub.3 2-CH.sub.3 4-CH.sub.3 60.89 4.68 5.92 61.13     4.83 6.05 17 C.sub.24 H.sub.22 Cl.sub.2 N.sub.2      O.sub.3 2-Cl O 3,5,6-CH.sub.3 ClCH.sub.3 3-CH.sub.3 5-CH.sub.3 63.03     4.85 6.12 62.64 4.73 6.40 18 C.sub.24 H.sub.22 Cl.sub.2 N.sub.2 O.sub.2     S 2-Cl S 3,6-(CH.sub.3 ).sub.25-Cl 3-CH.sub.3 5-CH.sub.3 60.89 4.68 5.92     61.12 4.73 5.94 19 C.sub.24 H.sub.21 Cl.sub.3 N.sub.2      O.sub.3 2,6-Cl.sub.2 O 3,6-(CH.sub.3).sub.25-Cl 3-CH.sub.3 5-CH.sub.3     58.61 4.30 5.70 58.41 4.26 5.71 20 C.sub.24 H.sub.21 ClF.sub.2 N.sub.2     O.sub.3 2,6-F.sub.2 O 3,6-(CH.sub.3).sub.25-Cl 3-CH.sub.3 5-CH.sub.3     62.82 4.61 6.10 63.23 4.67 6.08 21 C.sub.26 H.sub.26 Cl.sub.2 N.sub.2     O.sub.3 2-Cl O 3,6-(CH.sub.3).sub.25-Cl H 4-t-butyl 64.34 5.40 5.77     64.03 5.36 5.98 22 C.sub.26 H.sub.26 Cl.sub.2 N.sub.2 O.sub.2 S 2-Cl S     3,6-(CH.sub.3).sub.25-Cl H 4-t-butyl 62.27 5.23 5.59 62.06 5.43 5.79 23     C.sub.26 H.sub.25 Cl.sub.3 N.sub.2      O.sub.3 2,6-Cl.sub.2 O 3,6-(CH.sub.3).sub.25-Cl H 4-t-butyl 60.07 4.85     5.39 60.25 4.92 5.50 24 C.sub.26 H.sub.25 ClF.sub.2 N.sub.2 O.sub.3     2,6-F.sub.2 O 3,6-(CH.sub.3).sub.25-Cl H 4-t-butyl 64.14 5.17 5.75 64.40     5.32 5.73 25 C.sub.23 H.sub.20 Cl.sub.2 N.sub.2      O.sub.3 2-Cl O 3,6-(CH.sub.3).sub.25-Cl H 4-CH.sub.3 62.31 4.55 6.32     62.22 4.66 6.23 26 C.sub.23 H.sub.20 Cl.sub.2 N.sub.2 O.sub.2 S 2-Cl S     3,6-(CH.sub.3).sub.25-Cl H 4-CH.sub.3 60.13 4.39 6.10 59.84 4.38 5.98 27     C.sub.23 H.sub.19 Cl.sub.3 N.sub.2      O.sub.3 2,6-Cl.sub.2 O 3,6-(CH.sub.3).sub.25-Cl H 4-CH.sub.3 57.82 4.01     5.86 58.09 4.02 5.85 28 C.sub.23 H.sub.19 ClF.sub.2 N.sub.2 O.sub.3     2,6-F.sub.2 O 3,6-(CH.sub.3).sub.25-Cl H 4-CH.sub.3 62.10 4.30 6.30     62.05 4.41 6.19 29 C.sub.23 H.sub.20 Cl.sub.2 N.sub.2 O.sub.3 2-Cl O     3,6-(CH.sub.3).sub.25-Cl H 2-CH.sub.3 62.31 4.55 6.32 61.83 4.56 6.34 30     C.sub.23 H.sub.19 ClF.sub.2 N.sub.2      O.sub.3 2,6-F.sub.2 O 3,6-(CH.sub.3).sub.25-Cl H 2-CH.sub.3 62.10 4.30     6.30 62.02 4.50 6.79 31 C.sub.23 H.sub.20 Cl.sub.2 N.sub.2 O.sub.2 S     2-Cl S 3,6-(CH.sub.3).sub.25-Cl H 2-CH.sub.3 60.13 4.39 6.10 60.72 4.66     6.08 32 C.sub.23 H.sub.19 Cl.sub.3 N.sub.2 P.sub.3 2,6-Cl.sub.2 O     3,6-(CH.sub.3).sub.25-Cl H 2-CH.sub.3 57.82 4.01 5.86 57.95 4.22 5.95 33     C.sub.23 H.sub.19 BrCl.sub.2 N.sub.2      O.sub.3 2-Cl O 3,6-(CH.sub.3).sub.25-Cl 4-Br 2-CH.sub.3 52.90 3.67 5.36     53.18 3.68 5.47 34 C.sub.23 H.sub.19 BrClFN.sub.2 O.sub.2 S 2-F S     3,6-(CH.sub.3).sub.25-Cl 4-Br 2-CH.sub.3 52.94 3.67 5.37 53.13 3.68 5.37     35 C.sub.23 H.sub.18 BrCl.sub.3 N.sub.2      O.sub.2 2,6-Cl.sub.2 O 3,6-(CH.sub.3).sub.25-Cl 4-Br 2-CH.sub.3 49.62     3.26 5.03 49.60 3.29 4.99 36 C.sub.23 H.sub.19 BrCl.sub.2 N.sub.2     O.sub.2 S 2-Cl S 3,6-(CH.sub.3).sub.25-Cl 4-Br 2-CH.sub.3 51.32 3.56     5.20 51.63 3.53 5.20 37 C.sub.23 H.sub.18 BrClF.sub.2 N.sub.2 O.sub.3     2,6-F.sub.2 O 3,6-(CH.sub.3).sub.25-Cl 4-Br 2-CH.sub.3 52.75 3.46 5.35     52.27 3.40 5.43 38 C.sub.23 H.sub.19 BrCl.sub.2 N.sub.2 O.sub.3 2-Cl O     3,6-(CH.sub.3).sub.25-Cl 2-Br 4-CH.sub.3 52.90 3.67 5.36 52.43 3.68 5.31     39 C.sub.23 H.sub.18 BrCl.sub.3 N.sub.2      O.sub.3 2,6-Cl.sub.2 O 3,6-(CH.sub.3).sub.25-Cl 2-Br 4-CH.sub.3 49.62     3.26 5.03 49.75 3.23 5.00 40 C.sub.23 H.sub.18 BrClF.sub.2 N.sub. 2     O.sub.3 2,6-F.sub.2 O 3,6-(CH.sub.3).sub.25-Cl 2-Br 4-CH.sub.3 52.75     3.46 5.35 52.97 3.49 5.31 41 C.sub.23 H.sub.19 BrCl.sub.2 N.sub.2     O.sub.2 S 2-Cl S 3,6-(CH.sub.3).sub.25-Cl 2-Br 4-CH.sub.3 51.32 3.56     5.20 50.70 3.55 5.00 42 C.sub.23 H.sub.19 Cl.sub.3 N.sub.2 O.sub.3 2-Cl     O 3,6-(CH.sub.3).sub.25-Cl 4-Cl 2-CH.sub.3 57.82 4.01 5.86 57.51 4.00     5.66 43 C.sub.23 H.sub.18 Cl.sub.4 N.sub.2 O.sub.3 2,6-Cl.sub.2 O     3,6-(CH.sub.3).sub.25-Cl 4-Cl 2-CH.sub.3 53.93 3.54 5.49 54.22 3.55 5.55     44 C.sub.23 H.sub.18 Cl.sub.2 F.sub.2 N.sub.2 O.sub.3 2,6-F.sub.2 O     3,6-(CH.sub.3).sub.25-Cl 4-Cl 2-CH.sub.3 57.64 3.78 5.84 57.50 3.84 5.81     45 C.sub.23 H.sub.19 Cl.sub.3 N.sub.2 O.sub.2      S 2-Cl S 3,6-(CH.sub.3).sub.25-Cl 4-Cl 2-CH.sub.3 55.94 3.88 5.67 55.98     3.94 5.60 46 C.sub.23 H.sub.19 Cl.sub.3 N.sub.2      O.sub.3 2-Cl O 3,6-(CH.sub.3).sub.25-Cl 2-Cl 4-CH.sub.3 57.82 4.01 5.86     58.20 4.17 5.72 47 C.sub.23 H.sub.18 Cl.sub.4 N.sub.2      O.sub.3 2,6-Cl.sub. 2 O 3,6-(CH.sub.3).sub.25-Cl 2-Cl 4-CH.sub.3 53.93     3.54 5.49 53.91 3.51 5.50 48 C.sub.23 H.sub.18 Cl.sub.2 F.sub.2 N.sub.2     O.sub.3 2,6-F.sub.2 O 3,6-(CH.sub.3).sub.25-Cl 2-Cl 4-CH.sub.3 57.64     3.78 5.84 57.82 3.84 5.73 49 C.sub.23 H.sub.19 Cl.sub.3 N.sub.2 O.sub.2     S 2-Cl S 3,6-(CH.sub.3).sub.25-Cl 2-Cl 4-CH.sub.3 55.94 3.88 5.67 55.78     3.91 5.55 50 C.sub.31 H.sub.36 Cl.sub.2 N.sub.2      O.sub.3 2-Cl O 3,6-(CH.sub.3).sub.25-Cl H 4-n-C.sub.9 H.sub.19 67.02     6.53 5.04 66.06 6.47 5.14 51 C.sub.31 H.sub.35 Cl.sub.3 N.sub.2 O.sub.3     2,6-Cl.sub.2 O 3,6-(CH.sub.3).sub.25-Cl H 4-n-C.sub.9 H.sub.19 63.11     5.98 4.75 60.04 5.58 5.03 52 C.sub.31 H.sub.36 Cl.sub.2 N.sub.2 O.sub.2     S 2-Cl S 3,6-(CH.sub.3).sub.25-Cl H 4-n-C.sub.9 H.sub.19 65.14 6.35 4.90     64.36 6.35 4.86 53 C.sub.25 H.sub.25 ClN.sub.2 O.sub.2 S 2-CH.sub.3 S     3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.3 4-CH.sub.3 66.28 5.56 6.18 65.12     5.73 5.98 54 C.sub.24 H.sub.22 ClFN.sub.2      O.sub.2 S 2-F S 3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.3 4-CH.sub.3 63.08     4.85 6.13 62.91 4.83 6.14 55 C.sub.31 H.sub.35 ClF.sub.2 N.sub.2 O.sub.3     2,6-F.sub.2 O 3,6-(CH.sub.3).sub.25-Cl H 4-n-CaH.sub.19 66.84 6.33 5.03     66.16 6.48 4.78 56 C.sub.27 H.sub.28 Cl.sub.2 N.sub.2 O.sub.3 2-Cl O     3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.3 4-t-butyl 64.93 5.65 5.61 64.85 5.71     5.56 57 C.sub.27 H.sub.27 ClF.sub.2 N.sub.2 O.sub.3 2,6-F.sub.2 O     3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.3 4-t-butyl 64.74 5.43 5.59 64.70 5.73     5.65 58 C.sub.27 H.sub.28 Cl.sub.2 N.sub.2 O.sub.2      S 2-Cl S 3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.3 4-t-butyl 62.91 5.48 5.43     62.96 5.58 5.38 59 C.sub.27 H.sub.28 ClFN.sub.2 O.sub.2      S 2-F S 3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.3 4-t-butyl 64.98 5.66 5.61     65.24 5.85 5.52 60 C.sub.25 H.sub.24 Cl.sub.2 N.sub.2 O.sub.3 2-Cl O     3,6-(CH.sub.3).sub.25-Cl 2,3-(CH.sub.3).sub.2 5-CH.sub.3 63.69 5.13 5.94     63.68 5.30 5.99 61 C.sub.25 H.sub.23 Cl.sub.3 N.sub.2      O.sub.3 2,6-Cl.sub.2 O 3,6-(CH.sub. 3).sub.25-Cl 2,3-(CH.sub.3).sub.2     5-CH.sub.3 59.36 4.58 5.54 59.52 4.82 5.47 62 C.sub.25 H.sub.23 Cl.sub.2     FN.sub.2 O.sub.3 2,6-ClF O 3,6-(CH.sub.3).sub.25-Cl 2,3-(CH.sub.3).sub.2     5-CH.sub.3 61.35 4.74 5.72 61.49 4.81 5.77 63 C.sub.25 H.sub.23      ClF.sub.2 N.sub.2 O.sub.3 2,6-F.sub.2 O 3,6-(CH.sub.3).sub.25-Cl     2,3-(CH.sub.3).sub.2 5-CH.sub.3 63.49 4.90 5.92 63.58 5.20 5.92 64     C.sub.25 H.sub.24 Cl.sub.2 N.sub.2 O.sub.2      S 2-Cl S 3,6-(CH.sub.3).sub.25-Cl 2,3-(CH.sub.3).sub.2 5-CH.sub.3 61.59     4.96 5.75 61.78 5.12 5.77 65 C.sub.25 H.sub.24 ClFN.sub.2 O.sub.2 S 2-F     S 3,6-(CH.sub.3).sub.25-Cl 2,3-(CH.sub.3).sub.2 5-CH.sub.3 63.74 5.14     5.95 63.85 5.22 5.94 66 C.sub.26 H.sub.27 ClN.sub.2 O.sub.2 S 2-CH.sub.3     S 3,6-(CH.sub.3).sub.25-Cl 2,3-(CH.sub.3).sub.2 5-CH.sub.3 66.86 5.83     6.00 67.35 5.86 5.91 67 C.sub.25 H.sub.24 Cl.sub.2 N.sub.2 O.sub.3 2-Cl     O 3,6-(CH.sub.3).sub.25-Cl 3,4-(CH.sub.3).sub.2 5-CH.sub.3 63.69 5.13     5.94 63.68 5.21 5.87 68 C.sub.25 H.sub.23 Cl.sub.3 N.sub.2 O.sub.3     2,6-Cl.sub.2 O 3,6-(CH.sub.3).sub.25-Cl 3,4-(CH.sub.3).sub.2 5-CH.sub.3     59.36 4.58 5.54 59.68 4.80 5.31 69 C.sub.25 H.sub.23 Cl.sub.2 FN.sub.2     O.sub.3 2,6-ClF O 3,6-(CH.sub.3).sub.25-Cl 3,4-(CH.sub.3).sub.2 5-CH.sub.     3 61.35 4.74 5.72 61.60 4.84 5.79 70 C.sub.25 H.sub.23 ClF.sub.2 N.sub.2     O.sub.3 2,6-F.sub.2 O 3,6-(CH.sub.3).sub.25-Cl 3,4-(CH.sub.3).sub.2     5-CH.sub.3 63.49 4.90 5.92 63.35 4.97 5.83 71 C.sub.25 H.sub.24 Cl.sub.2     N.sub.2 O.sub.2 S 2-Cl S 3,6-(CH.sub.3).sub.25-Cl 3,4-(CH.sub.3).sub.2     5-CH.sub.3 61.59 4.96 5.75 61.65 5.05 5.70 72 C.sub.25 H.sub.24      ClFN.sub.2 O.sub.2      S 2-F S 3,6-(CH.sub.3).sub.25-Cl 3,4-(CH.sub.3).sub.2 5-CH.sub.3 63.74     5.14 5.95 64.29 5.17 5.91 73 C.sub.26 H.sub.27 ClN.sub.2 O.sub.2 S     2-CH.sub.3 S 3,6-(CH.sub.3).sub.25-Cl 3,4-(CH.sub.3).sub.2 5-CH.sub.3     66.86 5.83 6.00 67.60 6.13 6.13 74 C.sub.25 H.sub.24 Cl.sub.2 N.sub.2     O.sub.3 2-6 O 3,6-(CH.sub.3).sub.25-Cl H 2-i-C.sub.3 H.sub.7 63.70 5.13     5.94 63.94 5.26 5.87 75 C.sub.25 H.sub.23 ClF.sub.2 N.sub.2 O.sub.3     2,6-F.sub.2 O " H 2-i-C.sub.3 H.sub.7 63.50 4.90 5.92 63.36 5.08 5.80 76     C.sub.25 H.sub.25 ClN.sub.2      O.sub.3 2-CH.sub.3 O 3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.3 4-CH.sub.3     68.72 5.77 6.41 67.84 5.65 6.30 77 C.sub.24 H.sub.12 ClFN.sub.2 O.sub.3     2-F O " " " 65.38 5.03 6.35 65.25 5.13 6.21 78 C.sub.25 H.sub.26 N.sub.2     O.sub.3 2-CH.sub.3 O 3,5-(CH.sub.3).sub.2 " " 74.60 6.51 6.96 74.81 6.66     6.88 79 C.sub.25 H.sub.26 N.sub.2 O.sub.2 S 2-CH.sub.3 O " " " 71.74     6.26 6.69 72.14 6.42 6.54 80 C.sub.24 H.sub.23 FN.sub.2 O.sub.3 2-F O "     " " 70.92 5.70 6.89 71.09 5.70 6.98 81 C.sub.24 H.sub.22 Cl.sub.2     N.sub.2 O.sub.4 2-Cl O 3,6(CH.sub.3).sub.25-Cl 2-OCH.sub.3 4-CH.sub.3     60.90 4.68 5.92 60.85 4.57 5.84 82 C.sub.24 H.sub.21 Cl.sub.3 N.sub.2     O.sub.4 2,6-Cl.sub.2 O " " " 56.77 4.17 5.52 56.53 4.14 5.37 83 C.sub.24     H.sub.21 Cl.sub.2 FN.sub.2 O.sub.4 2,6-ClF O 3,6-(CH.sub.3).sub.2     2-OCH.sub.3 4-CH.sub.3 58.67 4.31 5.70 59.07 4.47 5.63 84 C.sub.24     H.sub.21 ClF.sub.2 H.sub.2 O.sub.4 2,6-F.sub.2 O " " " 60.70 4.46 5.90     60.98 4.19 5.72 85 C.sub.25 H.sub.25 ClN.sub.2 O.sub.4 2-CH.sub.3 O " "     " 66.29 5.56 6.18 66.57 5.56 6.29 86 C.sub.24 H.sub.22 ClFN.sub.2     O.sub.3 S 2-F S " " " 60.95 4.69 5.93 60.63 4.58 5.71 87 C.sub.24     H.sub.23 ClN.sub.2 O.sub.2 S 2-Cl S 3,5-(CH.sub.3).sub.2 2-CH.sub.3     4-CH.sub.3 65.67 5.28 6.38 66.09 5.50 6.27 88 C.sub.24 H.sub.22 Cl.sub.2     N.sub.2 O.sub.3 S 2-Cl O 3,6-(CH.sub.3).sub.25-Cl 4-SCH.sub.3 3-CH.sub.3     58.90 5.43 5.72 58.63 4.58 5.68 89 C.sub.24 H.sub.21 ClF.sub.2 N.sub.2     O.sub.3 S 2,6-F.sub.2 O " " " 58.72 4.31 5.71 58.62 4.29 5.91 90     C.sub.26 H.sub. 27 Cl.sub.2 N.sub.3      O.sub.3 2-Cl O " 3-CH.sub.3,4-N(CH.sub.3).sub.2 5-CH.sub.3 62.40 5.44     8.40 62.56 5.44 8.52 91 C.sub.26 H.sub.26 ClF.sub.2 N.sub.3 O.sub.3     2,6-F.sub.2 O 3,6-(CH.sub.3).sub.25-CL 3-CH.sub.3,4-N(CH.sub.3).sub.2     5-CH.sup.3 62.22 5.22 8.37 62.81 4.93 8.20 92 C.sub.26 H.sub.26 Cl.sub.3     N.sub.3 O.sub.3 2,6-Cl.sub.2 O " " " 58.38 4.90 7.86 58.28 5.02 7.99 93     C.sub.26 H.sub.26 Cl.sub.2 FN.sub.3 O.sub.3 2,6-ClF O " " " 60.24 5.06     8.10 60.15 5.13 7.77 94 C.sub.26 H.sub.27 ClFN.sub.3 O.sub.3 2-F O " " "     64.52 5.62 8.68 64.57 5.63 8.64 95 C.sub.27 H.sub.30 ClN.sub.3 O.sub.3     2-CH.sub.3 O " " " 67.56 6.30 8.75 67.21 6.38 8.38 96 C.sub.23 H.sub.20     Cl.sub.2 N.sub.2 O.sub.3 2-Cl O 2-CH.sub.35-Cl 2-CH.sub.3 4-CH.sub.3     62.31 4.55 6.32 62.65 4.92 6.27 97 C.sub.23 H.sub.19 ClF.sub.2 N.sub.2     O.sub.3 2,6-F.sub.2 O " " " 62.10 4.31 6.30 62.45 4.78 6.30 98 C.sub.22     H.sub.17 BrCl.sub.2 N.sub.2      O.sub.0 2-Cl O 2-CH.sub.35-Cl 4-Br 2-CH.sub.3 51.99 3.37 5.51 52.51     3.49 5.56 99 C.sub.22 H.sub.16 BrClF.sub.2 N.sub.2 O.sub.3 2,6-F.sub.2 O     C-CH.sub.35-Cl 4-Br 2-CH.sub.3 51.84 3.16 5.50 51.70 3.32 5.37 100     C.sub.23 H.sub.20 BrClN.sub.2 O.sub.3 2-Cl O 3-CH.sub.3 2-CH.sub.34-Br     6-CH.sub.3 56.58 4.13 5.74 57.19 4.34 5.77 101 C.sub.23 H.sub.19     BrF.sub.2 N.sub.2 O.sub.3 2,6-F.sub.2 O 3-CH.sub.3 2-CH,4-Br 6-CH.sub.3     56.41 3.91 5.72 56.96 4.14 5.66 102 C.sub.23 H.sub.20 Cl.sub.2 N.sub.2     O.sub.3 2-CH.sub.3 O 2-CH.sub.35-Cl 4-Cl 2-CH.sub.3 62.31 4.55 6.32     62.36 4.51 6.38 103 C.sub.24 H.sub.23 ClN.sub.2 O.sub.3 2-CH.sub.3 O     2-CH.sub.35-Cl 4-CH.sub.3 2-CH.sub.3 68.16 5.48 6.62 68.37 5.55 6.53 104     C.sub.23 H.sub.20 ClFN.sub.2 O.sub.3 2-F O 2-CH.sub.35-Cl 4-CH.sub.3     2-CH.sub.3 64.72 4.72 6.56 65.29 4.77 6.63 105 C.sub.22 H.sub.17     Cl.sub.3 FN.sub.2 O.sub.3 2-F O 2-CH.sub.35-Cl 4-Cl 2-CH.sub.3 59.08     3.83 6.26 59.48 3.80 6.24 106 C.sub.23 H.sub.20 BrFN.sub.2 O.sub.3 2-F O     3-CH.sub.3 4-Br6-CH.sub.3 2-CH.sub.3 58.56 4.27 5.94 59.37 4.43 5.82 107     C.sub.24 H.sub.23 BrN.sub.2      O.sub.3 2-CH.sub.3 O 3-CH.sub.3 4-Br6-CH.sub.3 2-CH.sub.3 61.62 4.96     5.99 62.83 5.22 5.85 108 C.sub.22 H.sub.17 BrClFN.sub.2 O.sub.3 2-F O     2-CH.sub.35-Cl 4-Br 2-CH.sub.3 53.74 3.48 5.70 53.75 3.59 5.43 109     C.sub.23 H.sub.20 BrClN.sub.2 O.sub.3 2-CH.sub.3 O 2-CH.sub.35-Cl 4-Br     2-CH.sub.3 56.63 4.13 5.74 56.84 4.09 5.64 110 C.sub.23 H.sub.20     BrClN.sub.2 O.sub.3 2-Cl O 3,5-(CH.sub.3).sub.2 4-Br 2-CH.sub.3 56.63     4.13 5.74 56.64 4.16 5.64 111 C.sub.23 H.sub.20 BrFN.sub.2 O.sub.3 2-F O     3,5-(CH.sub.3).sub.2 4-Br 2-CH.sub.3 58.61 4.28 5.94 58.59 4.54 5.79 112     C.sub.23 H.sub.19 BrClFN.sub.2 O.sub.3 2-Cl6-F O 3,5-(CH.sub.3).sub.2     4-Br 2-CH.sub.3 54.62 3.79 5.54 54.66 3.82 5.50 113 C.sub.23 H.sub.19     BrF.sub.2 N.sub.2 O.sub.3 2,6-F.sub.2 O 3,5-(CH.sub.3).sub.2 4-Br     2-CH.sub.3 56.46 3.91 5.72 56.61 4.30 5.61 114 C.sub.23 H.sub.19     BrClFN.sub.2 O.sub.3 2,6-ClF O 2,5-(CH.sub.3).sub.2 4-Br 2-CH.sub.3     54.62 3.79 5.54 54.96 3.90 5.36 115 C.sub.23 H.sub.18 BrF.sub.2 N.sub.2     O.sub.3 2,6-F.sub.2 O 2,5-(CH.sub.3).sub.2 4-Br 2-CH.sub.3 56.46 3.91     5.72 56.76 4.07 5.59 116 C.sub.23 H.sub.20 BrClN.sub.2 O.sub.3 2-Cl O     2,5-(CH.sub.3).sub.2 4-Br 2-CH.sub.3 56.63 4.13 5.74 56.64 4.20 5.64 117     C.sub.23 H.sub.20 Cl.sub.2 N.sub.2 O.sub.3 2-Cl O 2,5-(CH.sub.3).sub.2     2-Cl 4-CH.sub.3 62.31 4.55 6.32 62.21 4.69 6.09 118 C.sub.23 H.sub.20     ClFN.sub.2 O.sub.3 2-F O 1,5-(CH.sub.3).sub.2 2-Cl 4-CH.sub.3 64.72 4.55     6.32 64.93 4.82 6.54 119 C.sub.24 H.sub.23 ClN.sub.2 O.sub.3 2-CH.sub.3     O 2,5-(CH.sub.3).sub.2 2-Cl 4-CH.sub.3 68.16 5.48 6.62 68.20 5.61 6.62     120 C.sub.24 H.sub.23 ClN.sub.2      O.sub.3 H.sub.2 O 3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.3 4-CH.sub.3 68.16     5.48 6.62 68.01 5.78 6.42 121 C.sub.23 H.sub.20 BrClN.sub.2 O.sub.3     H.sub.2 O 3,6-(CH.sub.3).sub.25-Cl 4-Br 2-CH.sub. 3 56.63 4.13 5.74     57.07 4.56 5.69 122 C.sub.24 H.sub.22 ClFN.sub.2      O.sub.3 2-F O 3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.3 5-CH.sub.3 65.38 5.03     6.35 65.74 5.17 6.25 123 C.sub.24 H.sub.22 Cl.sub.2 N.sub.2 O.sub.3 2-Cl     O 3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.3 5-CH.sub.3 63.03 4.85 6.12 63.14     5.13 6.06 124 C.sub.24 H.sub.21 ClF.sub.2 N.sub.2 O.sub.3 2,6-F.sub.2 O     3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.3 5-CH.sub.3 62.86 4.62 6.11 62.90     4.67 6.01 125 C.sub.25 H.sub.25 ClN.sub.2      O.sub.3 2-CH.sub.3 O 3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.3 5-CH.sub.3     68.72 5.77 6.41 68.94 5.66 6.27 126 C.sub.26 H.sub.26 Cl.sub.2 N.sub.2     O.sub.3 2-Cl O 2-CH.sub.35-Cl 2-CH.sub.3 4-t-butyl 64.34 5.40 5.77 64.93     5.49 5.73 127 C.sub.26 H.sub.26 ClFN.sub.2 O.sub.3 2-F O 2-CH.sub.35-Cl     2-CH.sub.3 4-t-butyl 66.59 5.59 5.97 66.81 5.72 5.91 128 C.sub.26     H.sub.25 ClF.sub.2 N.sub.2      O.sub.3 2,6-F.sub.2 O 2-CH.sub.35-Cl 2-CH.sub.3 4-t-butyl 64.13 5.18     5.75 64.36 5.24 5.72 129 C.sub.27 H.sub.29 ClN.sub.2 O.sub.3 2-CH.sub.3     O 2-CH.sub.35-Cl 2-CH.sub.3 4-t-butyl 69.74 6.29 6.02 69.85 6.41 5.98     130 C.sub.26 H.sub.26 Cl.sub.2 N.sub.2      O.sub.3 2-Cl O 3,6-(CH.sub.3).sub.25-Cl H 2-s-butyl 64.34 5.40 5.77     63.51 5.28 6.07 131 C.sub.26 H.sub.26 ClFN.sub.2      O.sub.3 2-F O 3,6-(CH.sub.3).sub.25-Cl H 2-s-butyl 66.59 5.59 5.97     65.73 6.30 6.36 132 C.sub.26 H.sub.25 Cl.sub.2 FN.sub.2 O.sub.3 2-Cl,6-F     O 3,6-(CH.sub.3).sub.25-Cl H 2-s-butyl 62.04 5.00 5.56 61.06 4.86 5.79     133 C.sub.26 H.sub.25 ClF.sub.2 N.sub.2      O.sub.3 2,6-F.sub.2 O 3,6-(CH.sub.3).sub.25-Cl H 2-s-butyl 64.13 5.18     5.75 64.51 5.35 5.85 134 C.sub.24 H.sub.22 Cl.sub.2 N.sub.2 O.sub.3 2-Cl     O 3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.3 3-CH.sub.3 63.03 4.85 6.12 63.35     5.39 6.36 135 C.sub.24 H.sub.21 Cl.sub.2 FN.sub.2 O.sub.3 2-Cl,6-F O     3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.3 3-CH.sub.3 60.64 4.45 5.89 61.29     4.46 5.78 136 C.sub.24 H.sub.21 ClF.sub.2 N.sub.2 O.sub.3 2,6-F.sub.2 O     3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.3 3-CH.sub.3 62.82 4.61 6.10 63.04     4.89 6.21 137 C.sub.24 H.sub.21 Cl.sub.3 N.sub.2      O.sub.3 2-Cl O 3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.34-Cl 3-CH.sub.3 58.61     4.30 5.70 58.87 4.53 5.70 138 C.sub.24 H.sub.20 Cl.sub.3 FN.sub.2     O.sub.3 2-Cl,6-F O 3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.34-Cl 3-CH.sub.3     56.54 3.95 5.50 57.41 4.27 5.57 139 C.sub.24 H.sub.20 Cl.sub.2 F.sub.2     N.sub.2 O.sub.3 2,6-F.sub.2 O 3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.34-Cl     3-CH.sub.3 58.43 4.09 5.68 58.59 4.27 5.65 140 C.sub.23 H.sub.20     Cl.sub.2 N.sub.2 O.sub.3 2-Cl O 3-CH.sub.3 2-CH.sub.34-Cl 3-CH.sub.3     62.31 4.55 6.32 62.63 4.62 6.38 141 C.sub.23 H.sub.19 Cl.sub.2 FN.sub.2     O.sub.3 2-Cl6-F O 3-CH.sub.3 2-CH.sub.34-Cl 3-CH.sub.3 59.88 4.15 6.07     60.54 4.54 6.06 142 C.sub.23 H.sub.19 ClF.sub.2 N.sub.2      O.sub.3 2,6-F.sub.2 O 3-CH.sub.3 2-CH.sub.34-Cl 3-CH.sub.3 62.10 4.30     6.30 62.55 4.62 6.27 143 C.sub.24 H.sub.21 Cl.sub.3 N.sub.2 O.sub.3 2-Cl     O 3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.34-Cl 5-CH.sub.3 58.61 4.30 5.70     58.47 4.30 5.63 144 C.sub.24 H.sub.20 Cl.sub.3 FN.sub.2 O.sub.3 2-Cl,6-F     O 3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.35-Cl 5-CH.sub.3 56.54 3.95 5.50     56.88 4.05 5.39 145 C.sub.24 H.sub.20 Cl.sub.2 F.sub.2 N.sub.2 O.sub.3     2,6-F.sub.2 O 3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.34-Cl 5-CH.sub.3 58.43     4.09 5.68 58.72 4.18 5.68 146 C.sub.24 H.sub.21 Cl.sub.3 N.sub.2 O.sub.3     2-Cl O 3,6-(CH.sub.3).sub.25-Cl 3-CH.sub.34-Cl 5-CH.sub.3 58.61 4.30     5.70 58.59 4.34 5.53 147 C.sub.24 H.sub.20 Cl.sub.2 F.sub.2 N.sub.2     O.sub.3 2,6-F.sub.2 O 3,6-(CH.sub.3).sub.25-Cl 3-CH.sub.34-Cl 5-CH.sub.3     58.43 4.09 5.68 58.38 4.17 5.53 148 C.sub.24 H.sub.21 BrCl.sub.2 N.sub.2     O.sub.3 2-Cl O 3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.34Br 3-CH.sub.3 53.75     3.95 5.22 53.72 4.03 5.53 149 C.sub.24 H.sub.20 BrCl.sub.2 F.sub.2     N.sub.2 O.sub.3 2,6-F.sub.2 O 3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.34Br     3-CH.sub.3 53.60 3.75 5.21 53.27 3.78 5.07 150 C.sub.23 H.sub.20     BrCl.sub.2 N.sub.2 O.sub.3 2-Cl O 3-CH.sub.3 2-CH.sub.34Br 3-CH.sub.3     56.63 4.13 5.74 56.52 4.22 5.76 151 C.sub.23 H.sub.19 BrF.sub.2 N.sub.2     O.sub.3 2,6-F.sub.2 O 3-CH.sub.3 2-CH.sub.34Br 3-CH.sub.3 56.46 3.91     5.72 56.65 4.09 5.94 152 C.sub.23 H.sub.20 Cl.sub.2 N.sub.2 O.sub.3 2-Cl     O 3-CH.sub.3 2-CH.sub.34-Cl 5-CH.sub.3 62.31 4.55 6.32 62.17 4.65 6.30     153 C.sub.23 H.sub.19 Cl.sub.2 F.sub.2 N.sub.2 O.sub.3 2,6-F.sub.2 O     3-CH.sub.3 2-CH.sub.34-Cl 5-CH.sub.3 62.10 4.30 6.30 61.95 4.42 6.19 154 C     .sub.24 H.sub.21 BrF.sub.2 N.sub.2      O.sub.3 2,6-F.sub.2 O 3,5-(CH.sub.3).sub.2 2-CH.sub.34-Br 3-CH.sub.3     m.p. 194˜197° C. 155 C.sub.26 H.sub.25 BrCl.sub.2 N.sub.2     O.sub.3 2-Cl O 3,6-(CH.sub.3).sub.25-Cl 4-Br 2-s-butyl 55.34 4.46 4.96     55.49 4.42 4.87 156 C.sub.26 H.sub.24 BrClF.sub.2 N.sub.2 O.sub.3     2,6-F.sub.2 O 3,6-(CH.sub.3).sub.25-Cl 4-Br 2-s-butyl 55.19 4.28 4.95     55.78 4.28 4.81 157 C.sub.25 H.sub.22 ClF.sub.3 N.sub.2      O.sub.3 2-CF.sub.3 O 3,6-(CH.sub.3)5-Cl 2-CH.sub.3 4-CH.sub.3 61.17     4.52 5.71 61.45 4.66 5.63 158 C.sub.25 H.sub.24 Cl.sub.2 N.sub.2 O.sub.3     2-Cl O 3,6-(CH.sub.3).sub.25-Cl 2,4-(CH.sub.3).sub.2 5-CH.sub.3 63.70     5.13 5.94 63.64 5.24 6.03 159 C.sub.25 H.sub.23 ClF.sub.2 N.sub.2     O.sub.3 2,6-F.sub.2 O 3,6-(CH.sub.3).sub.25-Cl 2,4-(CH.sub.3).sub.2     5-CH.sub.3 63.50 4.90 5.92 63.75 5.18 6.63 160 C.sub.24 H.sub.21     Cl.sub.3 N.sub.2 O.sub.3 2-Cl O 3,6-(CH.sub.3).sub.25-Cl 2-Cl,4-CH.sub.3     5-CH.sub.3 58.61 4.30 5.70 59.19 4.68 5.60 161 C.sub.24 H.sub.20     Cl.sub.2 F.sub.2 N.sub.2 O.sub.3 2,6-F.sub.2 O 3,6-(CH.sub.3).sub.25-Cl     2-Cl,4-CH.sub.3 5-CH.sub.3 58.43 4.09 5.68 58.64 4.36 5.64 162 C.sub.23     H.sub.18 Cl.sub.4 N.sub.2 O.sub.4 2-Cl O 3,6-(CH.sub.3).sub.25-Cl     2,4-Cl.sub.2 5-CH.sub.3 53.93 3.54 5.47 54.16 3.79 5.41 163 C.sub.23     H.sub.17 Cl.sub.3 F.sub.2 N.sub.2      O.sub.3 2,6-F.sub.2 O 3,6-(CH.sub.3).sub.25-Cl 2,4-Cl.sub.2 5-CH.sub.3     53.77 3.34 5.45 53.57 3.42 5.58 164 C.sub.22 H.sub.16 BrCl.sub.3 N.sub.2     O.sub.3 2-Cl O 3,5-Cl.sub.2 2-CH.sub.3,4-Br 5-CH.sub.3 48.69 2.97 5.16     49.39 3.01 5.07 165 C.sub.22 H.sub.15 BrCl.sub.2 F.sub.2 N.sub.2 O.sub.3     2,6-F.sub.2 O 3,5-Cl.sub.2 2-CH.sub.3,4-Br 5-CH.sub.3 48.56 2.78 5.15     49.05 2.86 5.08 166 C.sub.24 H.sub.21 BrCl.sub.2 N.sub.2 O.sub.3 2-Cl O     3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.3,4-Br 5-CH.sub.3 53.75 3.76 5.22     53.96 4.04 5.20 167 C.sub.24 H.sub.20 BrClF.sub.2 N.sub.2 O.sub.3     2,6-F.sub.2 O 3,6-(CH.sub.3).sub.25-Cl 2-CH.sub.3,4-Br 5-CH.sub.3 53.60     3.75 5.21 53.69 3.78 5.16 168 C.sub.23 H.sub.20 Cl.sub.2 N.sub.2 O.sub.2     S 2-Cl S 2-CH.sub.35-Cl 2-CH.sub.3 4-CH.sub.3 60.13 4.39 6.10 60.58 4.55     6.05 169 C.sub.22 H.sub.17 Cl.sub.3 N.sub.2 O.sub.2      S 2-Cl S 2-CH.sub.35-Cl 4-Cl 2-CH.sub.3 55.07 3.57 5.84 55.86 3.61 5.64     170 C.sub.23 H.sub.20 Cl.sub.2 N.sub.2 O.sub.2      S 2-CH.sub.3 S 2-CH.sub.35-Cl 4-Cl 2-CH.sub.3 60.13 4.39 6.10 60.14     4.32 6.08 171 C.sub.24 H.sub. 23 BrN.sub.2 O.sub.2 S 2-CH.sub.3 S     3-CH.sub.3 2-CH.sub.3,4-Br 6-CH.sub.3 59.58 4.79 5.79 60.48 5.04 5.71     172 C.sub.22 H.sub.17 BrCl.sub.2 N.sub.2 O.sub.2      S 2-Cl S 2-CH.sub.3,5-Cl 4-Br 2-CH.sub.3 50.40 3.27 5.34 50.32 3.37     5.22 173 C.sub.23 H.sub.20 BrClN.sub.2 O.sub.2 S 2-Cl S 3-CH.sub.3     2-CH.sub.34-Br 6-CH.sub.3 54.78 4.00 5.56 55.82 4.37 5.04 174 C.sub.24     H.sub.23 ClN.sub.2 O.sub.2 S H.sub.2 S 3,6-(CH.sub.3).sub.2,5-Cl     2-CH.sub.3 4-CH.sub.3 65.67 5.28 6.38 66.57 5.41 6.35 175 C.sub.23     H.sub.20 Cl.sub.2 N.sub.2 O.sub.2 S H.sub.2 S 3,6-(CH.sub.3).sub.2,5-Cl     4-Cl 2-CH.sub.3 60.13 4.39 6.10 60.39 4.69 6.13 176 C.sub.24 H.sub.21     Cl.sub.3 N.sub.2 O.sub.2      S 2-Cl S 3,6-(CH.sub.3).sub.2,5-Cl 3-CH.sub.34-Cl 5-CH.sub.3 56.76 4.17     5.52 56.96 4.25 5.57 177 C.sub.24 H.sub.21 BrCl.sub.2 N.sub.2 O.sub.2 S     2-Cl S 3,6-(CH.sub.3).sub.2,5-Cl 2-CH.sub.34-Br 3-CH.sub.3 52.19 3.83     5.07 52.61 3.92 4.91 178 C.sub.23 H.sub.20 BrClN.sub.2 O.sub.2 S 2-Cl S     3-CH.sub.3 2-CH.sub.34-Br 3-CH.sub.3 54.83 4.00 5.56 54.98 4.18 5.57 179     C.sub.20 H.sub.20 Cl.sub.2 N.sub.2 O.sub.2                               4      S 2-Cl S 3-CH.sub.3 2-CH.sub.3-Cl 5-CH.sub.3 60.13 4.39 6.10 60.62 4.61     6.13 180 C.sub.26 H.sub.25 BrCl.sub.2 N.sub.2 O.sub.2      S 2-Cl S 3,6-(CH.sub.3).sub.2,5-Cl 4-Br 2-s-butyl 53.81 4.34 4.83 54.16     4.36 5.20 181 C.sub.24 H.sub.21 ClF.sub.2 N.sub.2 O.sub.2 S 2,6-F.sub.2     S 3,6-(CH.sub.3).sub.2,5-Cl 2-CH.sub.3 4-CH.sub.3 60.69 4.46 5.90 60.35     4.57 5.98 182 C.sub.24 H.sub.19 Cl.sub.2 N.sub.3      O.sub.3 2-Cl O 3,6-(CH.sub.3).sub.2,5-Cl 4-CN 2-CH.sub.3 61.55 4.09     8.97 61.68 4.48 8.32 183 C.sub.24 H.sub.18 ClF.sub.2 N.sub.3 O.sub.3     2,6-F.sub.2 O 3,6-(CH.sub.3).sub.2,5-Cl 4-CN 2-CH.sub.3 61.35 3.86 8.94     63.16 4.42 8.35 184 C.sub.25 H.sub.21 Cl.sub.2 N.sub.3 O.sub.3 2-Cl O     3,6-(CH.sub.3).sub.2,5-Cl 4-CN,5-CH.sub.3 2-CH.sub.3 62.25 4.39 8.71     62.21 4.59 8.50 185 C.sub.25 H.sub.20 ClF.sub.2 N.sub.3      O.sub.3 2,6-F.sub.2 O 3,6-(CH.sub.3).sub.2 ,5-Cl 4-CN,5-CH.sub.3     2-CH.sub.3 62.06 4.17 8.68 61.72 4.46 8.49 186 C.sub.26 H.sub.23     ClF.sub.2 N.sub.2 O.sub.5 2,6-F.sub.2 O 3,6-(CH.sub.3).sub.2,5-Cl     4-CO.sub.2 C.sub.2 H.sub.5 2-CH.sub.3 m.p. 176˜179° C. 187     C.sub.26 H.sub.24 Cl.sub.2 N.sub.2      O.sub.5 2-Cl O 3,6-(CH.sub.3).sub.2,5-Cl 4-CO.sub.2 C.sub.2 H.sub.5     2-CH.sub.3 m.p. 188˜190°      C.           Certain representative examples of the new compounds were evaluated     to determine their pesticidal activity against certain insects, including     a caterpiller and a beetle. The new compounds were also tested for     phtotoxicity on important economic crops including bean, soybean, corn,     tomato and cotton. The new compounds were further evaluated for mammalian     toxicity.

Suspensions of the test compounds were prepared by dissolving one gramof compound in 50 milliliters of acetone in which had been dissolved 0.1gram (10 percent of the weight of compound) of an alkylphenoxypolyethoyethanol surfactant, as an emulsifying or dispersing agent. Theresulting solution was mixed into 150 milliliters of water to giveroughly 200 milliliters of a suspension containing the compound infinely divided form. The thus-prepared stock suspension contained 0.5percent by weight of compound. The test concentrations in parts permillion by weight employed in the tests described hereinbelow wereobtained by appropriate dilutions of the stock suspension with water.The test procedures were as follows:

Southern Armyworm Leaf Spray Bait Test

Larvae of the southern armyworm (Spodoptera eridania, (Cram.)), rearedon Tendergreen bean plants at a temperature of 80°±5° F. and a relativehumidity of 50±5 percent, constituted the test insects.

The test compounds were formulated by diluting the stock suspension withwater to give a suspension containing 500 parts of test compound perTendergreen bean plants of standard height and age were placed on arevolving turntable and sprayed with 100-110 milliliters of testcompound formulation by use of a DeVilbiss spray gun set at 40 psig airpressure. This application, which lasted 25 seconds, was sufficient towet plants to run-off. As a control, 100-110 milliliters of awater-acetone-emulsifier solution containing no test compound were alsosprayed on infested plants. When dry, the paired leaves were separatedand each one was placed in a 9 centimeter Petri dish lined withmoistened filter paper. Five randomly selected larvae were introducedinto each dish and the dishes were closed. The closed dishes werelabeled and held at 80°-85° F. for three days. Although the larvae couldeasily consume the whole leaf within twenty-four hours, no more food wasadded. Larvae which were unable to move the length of the body, evenupon stimulation by prodding, were considered dead. Percent mortalitywas recorded for various concentration levels.

Mexican Bean Beetle Leaf Spray Test

Fourth instar larvae of the Mexican bean beetle (Epilachna varivestis,Muls.), reared on Tendergreen bean plants at a temperature of 80°±5° F.and 50±5 percent relative humidity, were the test insects.

The test compounds were formulated by diluting the stock suspension withwater to give a suspension containing 500 parts of test compound permillion parts of final formulation. Potted Tendergreen bean plants ofstandrd height and age were placed on a revolving turntable and sprayedwith 100-110 milliliters of test compound formulation by use of aDeVilbiss spray gun set at 40 psig air pressure. This application, whichlasted 25 seconds, was sufficient to wet plants to run-off. As acontrol, 100-110 milliliters of a water-acetone-emulsifier solutioncontaining no test compound were also sprayed on infested plants. Whendry, the paired leaves were separated and each was placed in a 9centimeter Petri dish lined with moistened filter paper. Five randomlyselected larvae were introduced into each dish, and the dishes wereclosed. The closed dishes were labeled and held at a temperature of80°±5° F., for three days. Although the larvae could easily consume theleaf within 24 to 48 hours, no more food was added. Larvae which wereunable to move the length of the body, even upon stimulation, wereconsidered dead.

Tobacco Budworm and Cotton Bollworm Leaf Spray Bait Test

Second instar larvae of the tobacco budworm (weighting about 4.5 mg)(Heliothis virescens, F.) and the cotton bollworm (weighing about 2.5mg) (Heliothis zea, (Boddie)), obtained commercially and reared onartificial diet at a temperature of 80°±5° F. and a relative humidity of50±5 percent, constituted the test insects.

Using a procedure similar to the above, but substituting cotten plantsfor snapbeans, treated and dried cotton leaves were introduced into 9 cmPetri dishes which were organized in to groups of 10-dish sets. Onerandomly selected larvae was introduced into each dish of a ten dish setand the dishes were closed. The closed dishes were labelled and held at80°±5° F. for five days.

The biological properties of certain representative examples of thecompounds of this invention are set forth in Table II below.

                  TABLE II                                                        ______________________________________                                        Biological Properties of Representative Benzoyl Ureas                                       Activity 500 ppm                                                Example         SAW.sup.(1)                                                                           MBB.sup.(2)                                           ______________________________________                                        1               A       A                                                     2               A       A                                                     3               A       A                                                     4               A       A                                                     5               A       A                                                     6               A       A                                                     7               A       A                                                     8               A       A                                                     9               A       A                                                     10              A       A                                                     11              A       A                                                     12              A       A                                                     13              A       A                                                     14              A       A                                                     15              A       A                                                     16              A       A                                                     17              A       A                                                     18              A       A                                                     19              A       A                                                     20              A       A                                                     21              A       A                                                     22              A       A                                                     23              A       A                                                     24              A       A                                                     25              A       A                                                     26              A       A                                                     27              A       A                                                     28              A       A                                                     29              A       A                                                     30              A       A                                                     31              A       A                                                     32              A       A                                                     33              A       A                                                     34              A       A                                                     35              A       A                                                     36              A       A                                                     37              A       A                                                     38              A       A                                                     39              A       A                                                     40              A       A                                                     41              A       A                                                     42              A       A                                                     43              A       A                                                     44              A       A                                                     45              A       A                                                     46              A       A                                                     47              A       A                                                     48              A       A                                                     49              A       A                                                     50              A       A                                                     53              A       A                                                     54              A       A                                                     55              A       A                                                     56              A       A                                                     57              A       A                                                     58              A       A                                                     59              A       A                                                     60              A       A                                                     61              A       A                                                     62              A       A                                                     63              A       A                                                     64              A       A                                                     66              A       A                                                     67              C       A                                                     68              C       A                                                     69              A       A                                                     70              A       A                                                     71              C       A                                                     72              C       A                                                     73              C       A                                                     74              A       A                                                     75              A       A                                                     76              A       A                                                     77              A       A                                                     78              A       A                                                     79              A       A                                                     80              A       A                                                     81              A       A                                                     82              A       A                                                     83              A       A                                                     84              A       A                                                     85              A       A                                                     86              A       A                                                     87              A       A                                                     88              A       A                                                     89              A       A                                                     90              C       A                                                     91              A       A                                                     92              C       A                                                     93              A       A                                                     94              A       A                                                     96              A       A                                                     97              A       C                                                     98              A       A                                                     99              A       A                                                     101             B       B                                                     102             A       A                                                     103             A       A                                                     104             A       A                                                     105             A       A                                                     106             A       B                                                     108             A       A                                                     109             A       A                                                     110             A       A                                                     111             A       A                                                     112             A       A                                                     113             A       A                                                     114             A       A                                                     115             A       A                                                     116             A       A                                                     117             A       A                                                     118             A       A                                                     119             A       C                                                     120             A       A                                                     121             A       C                                                     122             A       A                                                     123             A       A                                                     124             A       A                                                     125             A       A                                                     126             A       A                                                     127             A       A                                                     128             A       A                                                     129             A       A                                                     130             A       A                                                     131             A       A                                                     132             A       A                                                     133             A       A                                                     134             A       A                                                     135             A       A                                                     136             A       A                                                     137             A       A                                                     138             A       A                                                     139             A       A                                                     140             A       A                                                     141             A       A                                                     142             A       A                                                     143             A       A                                                     144             A       A                                                     145             A       A                                                     146             A       A                                                     147             A       A                                                     148             A       A                                                     149             A       A                                                     150             A       A                                                     151             A       A                                                     152             A       A                                                     153             A       A                                                     154             A       A                                                     155             A       A                                                     156             A       A                                                     157             A       A                                                     158             A       A                                                     159             A       A                                                     160             A       A                                                     161             A       A                                                     162             A       A                                                     163             A       A                                                     164             A       A                                                     165             A       A                                                     166             A       A                                                     167             A       A                                                     168             A       A                                                     169             A       A                                                     170             A       A                                                     172             A       A                                                     174             A       A                                                     175             A       A                                                     176             C       A                                                     177             A       A                                                     178             A       A                                                     179             A       A                                                     180             A       C                                                     181             A       A                                                     182             A       A                                                     183             A       A                                                     ______________________________________                                         .sup.(1) Southern Armyworm                                                    .sup.(2) Mexican Bean Beetle                                                  .sup.(3) Code = A = Complete control B = Moderate control C = No control 

EXAMPLES 212-217

In order to demonstrate the enhanced biological activity against theSouthern Armyworm, representative benzoyl ureas were compared with knownproducts. The results are set forth in Table III below:

                  TABLE III                                                       ______________________________________                                        Comparison Of Representative                                                  Benzoyl Ureas With                                                            Closely Related Prior Art                                                     Compounds Against Southern Armyworm                                                              Application                                                                             Percent Control                                  Compound           rate (ppm)                                                                              after 5 days                                     ______________________________________                                        1-(4-chlorophenyl)-3-                                                                            10        100                                              (2,6-difluorobenzoyl)urea.sup.(1)                                                                5         40                                               1-[4-(4-methylphenylthio)                                                                        500       40                                               phenyl]-3-(2,6-dichloro-                                                                         125       30                                               benzoyl)urea.sup.(2)                                                                             31        10                                               1-[4-(2,4-dimethylphenoxy)-                                                                      125       100                                              3-chlorophenyl]-3-(2-chloro-                                                                     31        30                                               benzoyl)urea.sup.(3)                                                                             8         20                                               1-[4-(2,4-dimethylphenoxy)-                                                                      2         100                                              3,6-dimethyl-5-chlorophenyl]-                                                                    1         100                                              3-(2-chlorobenzoyl)urea                                                       (Example #8)                                                                  1-[4-(2,4-dimethylphenoxy)-                                                                      2         100                                              3,6-dimethyl-5-chlorophenyl]-                                                                    1         90                                               3-(2-chlorobenzoyl)thiourea                                                   (Example #16)                                                                 1-[4-(2,4-dimethylphenoxy)                                                                       8         100                                              3,5-dimethylphenyl]-3-(2,6-                                                                      2         100                                              diflurorbenzoyl)urea (Example #4)                                             ______________________________________                                         .sup.(1) Dimilin ®, a known compound.                                     .sup.(2) a prior art compound. Ger. Offen 2,901,334.                          .sup.(3) a prior art compound. Ger. Offen. DE 3,104,407 (EP 57888)       

EXAMPLES 218-220

In order to demonstrate the enhanced biological activity againstHeliothis, representative benzoyl ureas were compared with knownproducts. The results are set forth in Table IV and V below:

                  TABLE IV                                                        ______________________________________                                        Comparison Of Representative Benzoyl Ureas                                    With Closely Related Prior Art                                                Compounds Against Heliothis zea                                                                       LD.sub.50 (ppm)                                       Compound                Heliothis zea                                         ______________________________________                                        1-(4-chlorophenyl)-3-                                                         (2,6-difluorobenzoyl)urea.sup.(1)                                                                     500                                                   1-[4-(4-methylphenylthio)phenyl]-                                                                     >100                                                  3-(2,6-dichlorobenzoyl)urea.sup.(2)                                           1-[4-(2,4-dimethylphenoxy)-3-                                                 chlorophenyl]-3-(2,6-difluoro-                                                                        >100                                                  benzoyl)urea.sup.(3)                                                          1-[4-(2,4,5-trimethylphenoxy)-                                                                        0.4                                                   3,6-dimethyl-5-chlorophenyl]-3-                                               (2,6-difluorobenzoyl)urea (Example #159)                                      1-[4-(2,5-dimethyl-4-chlorophenoxy)-                                                                  0.7                                                   3,6-dimethyl-5-chlorophenyl]-3-                                               (2,6-difluorobenzoyl)urea (Example #145)                                      ______________________________________                                         .sup.(1) Dimilin ®, a known compound                                      .sup.(2) a prior art compound. Ger. Offen 2,901,334.                          .sup.(3) a prior art compound. Ger. Offen. DE 3,104,407 (EP 57888)       

                  TABLE V                                                         ______________________________________                                        Comparison Of Representative Benzoyl Ureas                                    With Closely Related Prior Art                                                Compounds Against Heliothis virescens                                                                LD.sub.50 (ppm)                                        Compound               Heliothis virescens                                    ______________________________________                                        1-(4-chlorophenyl)-3-                                                         (2,6-difluorobenzoyl)urea.sup.(1)                                                                    31                                                     1-[4-(4-methylphenylthio)phenyl]-                                                                    >100                                                   3-(2,6-dichlorobenzoyl)urea.sup.(2)                                           1-[4-(2,4-dimethylphenoxy)-3-chloro-                                          phenyl]-3-(2,6-difluorobenzoyl)urea.sup.(3)                                                          >100                                                   1-[4-(2,5-dimethyl-4-chlorophenoxy)-                                                                 0.63                                                   3,6-dimethyl-5-chlorophenyl]-3-(2,6-                                          difluorobenzoyl)urea (Example #145)                                           1-[4-(2-methyl-4-t-butylphenoxy)-                                                                    2.4                                                    3,6-dimethyl-5-chlorophenyl]-3-                                               (2,6-difluorobenzoyl)urea (Example #57)                                       ______________________________________                                         .sup.(1) Dimilin ®, a known compound                                      .sup.(2) a prior art compound. Ger. Offen 2,901,334                           .sup.(3) a prior art compound. Ger. Offen. DE 3,104,407 (EP 57888)       

Although the invention has been illustrated by the foregoing examples,it is not to be construed as being limited to the materials employedtherein; but rather, the invention encompasses the generic area ashereinafter disclosed. Various modifications and embodiments can be madewithout departing from the spirit and scope thereof.

What is claimed is:
 1. A compound having the formula1-[4-(2,4-dimethylphenoxy)-3,6-dimethyl-5-chlorophenyl]-3-(2-chlorobenzoyl)urea.
 2. A compound having the formula1-[4-(2,4-dimethylphenoxy-)-3,6-dimethyl-5-chlorophenyl]-3-(2,6-difluorobenzoyl)urea.
 3. An insecticide composition comprising an acceptable carrier andan insecticidally effective amount of the compound of claim
 1. 4. Aninsecticide composition comprising an acceptable carrier and aninsecticidally effective amount of the compound of claim
 2. 5. A methodof controlling insects which comprises subjecting said insects to aninsecticidally effective amount of the compound of claim
 1. 6. A methodof controlling insects which comprises subjecting said insects to aninsecticidally effective amount of the compound of claim 2.